CN102143791B - 醛降低组合物 - Google Patents
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Abstract
提供从建筑物内部的空气中提高的除去醛的组合物。该组合物包括氨基硅烷和多价金属的碳酸盐,且特别地适合于加入到建筑产品板底材,例如隔音天花板面板和石膏墙壁中。可在制造过程中施加本发明的组合物,或者可后施加到已经构造的室内表面上。该组合物提供迄今为止没有实现过的醛除去的时间长度。
Description
相关申请的交叉参考
根据35U.S.C.§119(e),本申请要求2008年7月18日提交的标题为“AldehydeReducingCoating”的美国临时申请序列号No.61/135309的权益。
发明领域
本发明涉及内部建筑环境用材料,和具体地能降低内部建筑空间内挥发性有机化合物(VOC),例如醛含量的建筑材料。更具体地,与其他已知的醛降低剂相比,氨基硅烷(AS)和多价金属的碳酸盐(MVMC)的结合物在降低醛和迄今为止没有实现过的反应寿命方面预料不到地优异。
发明背景
在静态结构,例如房屋、商业建筑和学校中,宽泛的各种建筑材料和整理(finishing)材料通常用赋予降低VOC浓度的能力而设计的组合物涂布和/或浸渍。多孔建筑材料,例如由纤维、填料和粘合剂的浆料制备的天花板瓷砖底材是这种材料的例子。
在下述说明书中,甲醛用于VOC的说明目的,所述VOC包括其他醛。癌症研究的国际机构将醛分类为已知的致癌物。暴露于高浓度的甲醛,以及长期暴露在较低浓度下可引起潮湿(watery)的眼睛,眼睛、喉咙内灼烧感,难以呼吸和其他症状。通常常见的是人们对甲醛以及其他醛产生过敏性,从而导致皮肤瘙痒和hives等。在内部建筑环境中,因在建筑材料、木材产品、纺织品、家庭或办公室家具、纸张、化妆品、香烟烟雾、药物和室内清洁产品中使用甲醛,人们常常暴露于甲醛下。在新的建筑中,甲醛含量尤其高,这是因为从新的建筑材料中释放量高。因此,长期需要降低或消除内部建筑环境内的甲醛浓度。
常规的尝试包括,但不限于,与胺和其他甲醛反应性材料反应。此外,具体地在天花板瓷砖和石膏墙板底材领域中尝试在这些板由其制造的浆料的总配方中以及在施加到其上的涂料中包括甲醛降低添加剂。尽管通过这些反应体系实现了从空气中甲醛的一定降低,但甲醛降低的时间短。结果,需要更加有效的甲醛降低剂,和尤其具有长的效率显著降低甲醛的甲醛降低剂。
发明概述
本发明提供一种用于建筑材料,例如多孔底材和纤维素底材,以及其他建筑材料,例如金属和玻璃的醛降低组合物。本发明的组合物特别适合于加入到建筑产品板底材,例如隔音天花板面板和石膏墙板中。本发明的组合物可以在制造过程中施加,或者后施加到已经构造的室内表面上。
在一个例举的实施方案中,组合物配方包括水、氨基硅烷(氨丙基-三甲氧基硅烷)和多价金属碳酸盐的干燥产物。多价金属碳酸盐选自碳酸钙和碳酸镁。该组合物可任选地包括硅胶以实现甚至更大的醛降低作用。由下述说明可以证明,氨基硅烷和多价金属碳酸盐的结合物提供了迄今为止已知醛反应性体系没有实现的预料不到优异的性能谱。该组合物在迄今为止没有实现过的长时间段内提供较大的醛降低作用。此外,化学吸附反应导致醛永久地键合在组合物内,从而防止醛释放回空气内。甚至更加令人惊奇的是,当添加硅胶到氨基硅烷和多价金属的碳酸盐中时,可获得甚至更长期的效率。
附图简述
图1是显示甲醛降低%数据(Y)对于时间(X)的表5-8的示意图表。
图2是显示甲醛降低%数据(Y)对于时间(X)的表10的示意图表。
发明详述
本发明的组合物的主要成分是AS和MVMC,正如以下更加详细地列出的,将单氨基硅烷和二氨基硅烷各自加入到含有MVMC和具体地碳酸钙的涂料配方内。通过喷涂施加涂料,然而可通过任何其他方法,其中包括辊、刷子、辊涂、幕涂和刮刀式涂布,施加涂料。在涂料配方中具体地使用该体系时,固体含量范围为约1%-约90%,和优选约50%。本发明的组合物优选是水性的,然而,也可使用溶剂混合物,只要溶质可分散甲醛反应性添加剂即可。
将表1-4中列出的每一实施例的涂料配方施加到玻璃微纤维滤纸上,测试其甲醛除去能力和效率。在65L不锈钢环境测试腔室内,使用以下更加详细地描述的环境腔室试验,进行甲醛降低试验。首先一起混合水、氨基硅烷和任选地硅胶,形成湿混合物。然后,将除了粘合剂以外的其他添加剂加入到该湿混合物中。然后将粘合剂混合到已经含有其他添加剂的湿混合物内。
下表1阐述了第一实施例的涂料配方(配方#1)。
表1
固体=54%
填料/粘合剂之比=14.4
湿法施加=20g/ft2
干法施加=10.8g/ft2
计算的氨基硅烷施加=1.0g/ft2
计算的硅胶施加=2.0g/ft2
下表2阐述了不含硅胶的第二实施例的涂料配方(配方#2)。
表2
%固体=54
填料/粘合剂之比=14.4
湿法施加=20.0g/ft2
干法施加=10.8g/ft2
计算的氨基硅烷施加=1.0g/ft2
下表3阐述了不舍碳酸钙的第三实施例的涂料配方(配方#3)。
表3
%固体=16
湿法施加=20.0g/ft2
干法施加=3.2g/ft2
计算的氨基硅烷施加=1.0g/ft2
计算的硅胶施加=2.0g/ft2
下表4阐述了不含硅胶的第二实施例的涂料配方(配方#4)。
表4
成分 | 目的 | %湿重 | %干重 |
水 | 溶质 | 30.00 | 0 |
乙烯氯乙烯胶乳 | 粘合剂 | 7.33 | 6.80 |
二苯胺 | 抗氧化剂 | 1.00 | 0.92 |
聚丙烯酸钠 | 分散剂 | 0.08 | 0.15 |
硅酮消泡剂 | 消泡剂 | 0.06 | 0.12 |
碳酸钙浆料 | 填料 | 46.53 | 64.34 |
单氨基硅烷(氨丙基三乙氧基硅烷) | 醛反应物 | 5.00 | 9.27 |
硅胶 | 10.00 | 18.4 |
固体=54%
填料/粘合剂之比=14.4
湿法施加=20g/ft2
干法施加=10.8g/ft2
计算的氨基硅烷施加=1.0g/ft2
计算的硅胶施加=2.0g/ft2
氨基硅烷可选自三乙氧基硅烷,三甲氧基硅烷,甲基二乙氧基硅烷和甲基二甲氧基硅烷,或连接了氨基官能度的其他硅烷材料,它包括,但不限于,N-氨乙基-氨丙基三甲氧基硅烷,N-氨乙基-氨丙基三乙氧基硅烷,N-氨乙基-氨丙基甲基二甲氧基硅烷,N-氨乙基-氨丙基甲基二乙氧基硅烷,氨丙基三乙氧基硅烷,氨丙基-三甲氧基硅烷。
尽管优选的粘合剂是乙烯氯乙烯,但可使用任何常规的粘合剂。组合物可任选地含有小量的加工添加剂,其中包括表面活性剂、消泡剂、分散剂、增稠剂、杀虫剂和抗氧化剂。当这种胺基暴露于其中温度超过75℃的加热工艺下时,为了防止胺反应性基团氧化,例如,抗氧化剂、二苯基胺包括在上述配方内,但不要求它们来实现甲醛降低。因此,如果不要求干燥工艺加热,则抗氧化剂不是必须的。抗氧化剂可包括,但不限于,二苯胺,三(壬基苯基)亚磷酸酯,二苯甲酮磺酸,取代二苯甲酮,二(十三烷基)硫代二丙酸酯,和受阻酚类。
测量甲醛降低的方法
将与来自渗透烘箱的已知量的甲醛混合的净化空气在固定的流速下连续地引入到环境试验腔室内。将具有试验涂层的样品放置在该腔室内。试验腔室和空气维持在73.5F下,和空气的相对湿度为50%。根据ASTMD-5197试验方法,在各种时间间隔下测量在输出物流内的甲醛浓度。基于输入和输出的甲醛浓度差,估计甲醛的降低%。一般地,总的方法遵照ASTMD-5116和ISO16000-23(草稿)中提供的教导。
在2种水平的输入浓度-1.6ppm和0.1ppm下测定甲醛的降低程度。发现对于给定的样品大小来说,降低程度与输入浓度无关。但降低的持续时间与输入浓度成反比,和与样品大小直接成正比。这些结果证明甲醛与试验涂层按照一级反应动力学反应。
假设一级动力学,估计在0.013ppm的典型室温浓度下的甲酸降低时间长度。
转化:1.60ppm/0.013ppm/24h/天/365天/年=年数
表5
配方#1(甲醛输入1.60ppm)
时间(h) | 测量的(ppm) | 甲醛降低(%) |
0 | 1.60 | 0 |
24 | 0.092 | 94.52 |
48 | 0.086 | 94.88 |
72 | 0.081 | 95.18 |
144 | 0.092 | 94.52 |
样品大小:3×3英寸
空气湿度50%Rh
温度73.5F
空气流速=1.3空气变化/小时
表6
配方#2(甲醛输入1.60ppm)
时间(h) | 测量的(ppm) | 甲醛降低(%) |
0 | 1.60 | 0 |
24 | 0.14 | 91.3 |
72 | 1.47 | 8.70 |
168 | 1.60 | 0 |
样品大小:3×3英寸
空气湿度50%Rh
温度73.5F
空气流速=1.3空气变化/小时
表7
配方#3(甲醛输入1.60ppm)
时间(h) | 测量的(ppm) | 甲醛降低(%) |
0 | 1.60 | 0 |
24 | 0.24 | 85.0 |
48 | 0.32 | 80.0 |
72 | 0.40 | 75.5 |
144 | 0.45 | 71.9 |
样品大小:3×3英寸
空气湿度50%Rh
温度73.5F
空气流速=1.3空气变化/小时
表8
配方#4(甲醛输入1.60ppm)
时间(h) | 测量的(ppm) | 甲醛降低(%) |
0 | 1.60 | 0 |
24 | 0.12 | 92.50 |
48 | 0.16 | 90.00 |
72 | 0.20 | 87.50 |
144 | 0.21 | 86.87 |
样品大小:3×3英寸
空气湿度50%Rh
温度73.5F
空气流速=1.3空气变化/小时
图1中图示了表5-8。
图1所示的图表清楚地说明了本发明的体系在降低甲醛方面高度有效。令人惊奇的是,具有氨基硅烷和碳酸钙二者的配方#1、#2和#4清楚地显示出在长的时间段内高的醛含量降低能力的预料不到的显著改进。图1进一步阐述了对于长期甲醛降低来说,不具有硅胶的氨基硅烷和碳酸钙的结合物比单独的氨基硅烷和硅胶,即不具有碳酸钙的配方清楚地更加有效。此外,二氨基硅烷比单氨基硅烷清楚地更加有效。而且,表5和8的配方提供最好的结果,这反过来表明氨基硅烷、硅胶和多价金属碳酸盐协同除去甲醛且具有优异和预料不到的长期反应性。认为氨基硅烷在硅胶的表面区域上扩散,从而形成氨基硅烷的几乎单层,和确实形成这种单层,且不需要本领域中形成这种单层通常要求的化学接枝。与实际的机理无关,显示出这一行为的配方极其有效地改进内部建筑环境的空气质量。
可在制造建筑产品板底材中,施加本发明的组合物,或者后施加到已经构造的室内表面上。人们预期施加本发明的甲醛降低涂料与矿物纤维的隔音天花板瓷砖,例如获自ArmstrongWorldIndustries,Inc.的CIRRUS天花板瓷砖的整理涂料一样。以下解释为仅仅说明,决不是限制本发明公开内容的其余部分。在下述实施例中,所有份和百分数以重量计,除非另有说明。
将以上列出的配方#1施加到隔音天花板瓷砖上,和尤其CIRRUS天花板瓷砖上,并使用以上列出的试验方法测试。使用下述条件:甲醛输入=1.60;负载因子=0.40/m;相对湿度=50%;温度=25℃。
表9阐述了使用以上列出的转化,在0.013ppm的典型室内浓度下甲醛降低的时间长度。
表9
在1.60ppm下的时间(h) | 测量的(ppm) | 在0.013ppm下的时间(年)** |
0 | 1.600 | 0 |
24 | 0.121 | 0.34 |
72 | 0.119 | 1.01 |
144 | 0.130 | 2.02 |
216 | 0.150 | 3.03 |
312 | 0.240 | 4.38 |
384 | 0.450 | 5.40 |
480 | 0.900 | 6.74 |
552 | 1.110 | 7.76 |
650 | 1.350 | 9.13 |
720 | 1.416 | 10.12 |
816 | 1.450 | 11.46 |
888 | 1.490 | 12.48 |
984 | 1.500 | 13.83 |
**转化:1.60ppm/0.013ppm/24h/天/365天/年=年数
表10示出了在0.013ppm下甲醛降低的时间(年)。
表10
时间(年) | 甲醛降低(%) |
1 | 92% |
2 | 92% |
3 | 91% |
4 | 87% |
5 | 78% |
6 | 60% |
7 | 40% |
8 | 28% |
9 | 19% |
10 | 13% |
11 | 10% |
12 | 8% |
13 | 6% |
图2中图示了表10。根据表9中的上述数据可看出,令人惊奇的是,添加氨基硅烷和硅胶到MVMC基涂料中将提供内部空间最多约12年的时间长度的甲醛急剧降低。更具体地,对于含有氨基硅烷、MVMC和硅胶的体系来说,平均甲醛降低实现下述平均的甲醛降低:头一年94%;头5年内88%,头10年内降低60%,和头12年内降低55%。尽管众所周知的是在结构材料和整理剂中使用MVMC,例如碳酸钙和碳酸镁,但没有理由认为它与氨基硅烷的结合将提供提高的甲醛降低。
尽管参考优选的实施方案描述了本发明,但本领域的技术人员要理解,可在没有脱离本发明的范围情况下,可做出各种变化和用等价物替代其要素。另外,可在没有脱离本发明的基本范围的情况下,根据本发明的教导,做出许多改性,以适应特定的情形或材料。因此,打算本发明不限于所公开的特定实施方案作为实施本发明的最好模式,但本发明将包括落在所附权利要求氛围内的所有实施方案。
例如,尽管前述说明阐述了在施加到在内部建筑环境的表面上的涂料中使用本发明预料不到优异的醛降低体系,但可在建筑材料的芯,例如隔音矿物纤维面板或石膏墙板中使用该醛降低体系,且不打算限制其在涂料中使用。另外,尽管讨论和实施例涉及醛反应性物质的应用,当将它施加到天花板面板底材上时,但不要求实现前述预料不到的优异性能范围。醛反应性体系可用于墙壁内部或其上以及其他内部建筑材料上,因此该体系不打算限制到它在天花板面板底材内或其上使用。此外,如上所述,其他MVMC,例如碳酸镁可替代上述实施例中的碳酸钙。
Claims (14)
1.从空气中除去醛的组合物,该组合物包括氨基C1-2烷氧基硅烷和多价金属碳酸盐。
2.权利要求1的组合物,其中氨基C1-2烷氧基硅烷是二氨基C1-2烷氧基硅烷。
3.权利要求1的组合物,其中多价金属碳酸盐选自碳酸钙和碳酸镁。
4.权利要求1的组合物,进一步包括硅胶。
5.权利要求1的组合物,进一步包括粘合剂,选自:乙烯氯乙烯,环氧树脂,聚氨酯,聚酯,三聚氰胺,天然或改性天然聚合物,和乙酸乙烯酯、丙酸乙烯酯、丁酸乙烯酯,乙烯,氯乙烯,偏氯乙烯,氟乙烯,偏氟乙烯、丙烯酸乙酯、丙烯酸甲酯、丙烯酸丙酯、丙烯酸丁酯、甲基丙烯酸乙酯、甲基丙烯酸甲酯、甲基丙烯酸丁酯、甲基丙烯酸羟乙酯、苯乙烯、丁二烯和氨基甲酸酯的聚合物或共聚物。
6.权利要求5的组合物,其中粘合剂是乙烯氯乙烯。
7.权利要求1的组合物,其中在施加到建筑材料表面上的涂料中使用该组合物。
8.权利要求7的组合物,其中建筑材料是石膏板、矿物纤维板、玻璃纤维板、木材或木材复合材料、塑料、石膏、金属或纺织品。
9.权利要求7的组合物,其中可通过辊、刷子、辊涂、刮刀式涂布或幕涂施加涂料。
10.权利要求1的组合物,其中氨基C1-2烷氧基硅烷选自N-氨基乙基-氨基丙基-三甲氧基硅烷,N-氨基乙基-氨基丙基-三乙氧基硅烷,N-氨基乙基-氨基丙基甲基-二甲氧基硅烷,N-氨基乙基-氨基丙基甲基-二乙氧基硅烷,氨基丙基-三乙氧基硅烷和氨基丙基-三甲氧基硅烷。
11.权利要求1的组合物,其中组合物降低了从室内建筑环境的空气中挥发出的醛。
12.权利要求10的组合物,其中氨基C1-2烷氧基硅烷在硅胶上形成了单层。
13.权利要求12的组合物,其中该单层是在没有化学接枝的情况下形成的。
14.权利要求3的组合物,其中多价金属碳酸盐是碳酸钙。
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US9764307B2 (en) * | 2015-12-15 | 2017-09-19 | Awi Licensing Llc | VOC and odor reducing building panels |
US9702142B1 (en) | 2016-04-27 | 2017-07-11 | Awi Licensing Llc | Water stain and sag resistant acoustic building panel |
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US11865579B2 (en) | 2021-03-19 | 2024-01-09 | Usg Interiors, Llc | Hybrid coating process |
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US8598069B2 (en) | 2013-12-03 |
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